Process for breaking petroleum emulsions employing gluconic acid salts of oxyalkylated amine-modified thermoplastic phenol-aldehyde resins



2,771,446 PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING GLUCONIC ACID SALTS 0F OXYALKYLATED AlvilNE-MODIFIED THERMO- PLASTIC PHENOL-ALDEHYDE RESlNS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application January 26, 1953, Serial No. 333,387 36 (llaims. (Cl. 252-341) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,743, filed May 19, 1952, now abandoned; Serial No. 296,084, filed June 27, 1952, now U. S. Patent 2,679,485; Serial No. 301,804, filed July 30, 1952, now Patent No. 2,743,252; and Serial No. 310,552, filed September 19, 1952, now U. S. Patent 2,695,888; and Serial No. 329,483, filed January 2, 1953.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 310,552, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the Waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain oxyalkylated condensates of basic hydroxylated secondary monoamines with certain phenolaldehyde resins and formaldehyde therein described.

My present invention is concerned with demulsification which involves the use of the aforementioned oxyalkylated amino resin condensate in the form of a gluconic acid salt,.i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid which, for practical purposes, is as simple as analogous inorganic reactions.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufiicient hydro phile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a'water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there States Patent 0 will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with approximate basic secondary hydroxylated amines which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding; into the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts.

PART 1 The compounds used in accordance with the present invention are the gluconic acid salts of the products obtained by oxyalkylating the amine resin condensates described in applications Serial Nos. 288,743 and 296,084, to Which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. Such formula would be the following:

R R n R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and :2 generally is a small Whole number varying froml to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

in which R represents any appropriate hydrocarbon radical such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one of the radicals designated by R has at least one hydroxyl radical. The hydrocarbon radical may have the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not have a negative radical which considerably reduces the basicity of the amine such as an aryl radical or an acyl radical. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of described condensation products.

ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. The presence of one or more hydroxyl radicals introduces a significant hydrophile effect. Finally, in such cases where R contains, one or more oxygen atoms in the form of an ether linkage another effect is introduced, particularly another hydrophile effect. V

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or paraposition, i. e., the phenols themselves are difunctional phenols.

Theresins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points or" reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group. 7

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

g The resins herein employed as raw materials must be comparatively low mola'l products having on the average 3 to 6 nuclei per resin molecule. e

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities 1 is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperature going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the'two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in onephase or the other? Although reactions of the kind herein described will beginat least at comparatively iii) low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heatreactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. if this latter procedure is employed inp'reparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of Water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process .is not intended to limit the method or order inwhich the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin'molecu'le. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which-three different molecules are simultaneously involved although, for theoretical reasons, that is less likely; What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 i It is well known that one can readily purchase on the open market, or prepare fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH 7 OH 7 0H R P. R

In the above formula 12 represents a small whole number varying from 1 to.6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin .is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may,of course, be derived from any other reactive aldehyde having 8 carbon atoms or less. I

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde or only one mole of the amine may combine with the resin molecule, or even to a very slight extent if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid asa catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few lOths. of a percent. Sometimes moderate increases in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamerpresent. Thus, the molecular 6 weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. wt. of resin molecule (based on n+2) Example R number R II! derived n Phenyl Tertiary butyl Secondary butyl. Oyc1o-hexy1 I Tertiary amyl Mixed secondary and tertiary amyl.

Propyl Tertiary hexyl. Octyl menu:

Tertiary butyl.

Tertiary amyl Nonyl Tertiary butyl Tertiary amyl PART 3 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the. amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, ben- 2-amino-2-ethyl-1,3-propanediol,

. more divalent oxygen linkages as part of'an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularlyin two United States'patents, to wit, US.

Patents Nos. 2,325,514 dated July 27, '1943, to Hester, and 2,355,337 dated August 8,1944, to Spence. The latter patent describes typical haloalkyl ethers such as V 7 021150 021140021240 ciniooimci Such haloalkyl ethers can be reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

V 2 sOC2H4OCi 4) t HO CrHl (GsHnO Cz iO 021140 0 114) HO C2114 (CtHeO CH2CH OH3) 0 (CH3) OHCHz) HO C2H4 .(CHsOCHzOHzOOHzOHgOOHzOH a V B00211; (OHaOC 2C 2GH2C 2OH2CH2) 7 Nn HD0211; or comparable compounds having two hydroxylated groups of different lengths as in nocngonioongomocmom) amines such as glncamine, gelactamine and fructamine,

such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by V CH3 nocntc'cnzon rim no'onrbonion A i C Ha I itself.

CHa.C.CHzOH .onac nomon t.

' V i I CH3 See, also, corresponding hydroxylatedamines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063 dated June 6, 1950, to Bried. Still other examples are illustrated by treatmerit of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for'production of suitablecompounds having -a hydroxyl group and a single basic' amino nitrogen atom can be obtained from any suitable alcohol or the like by reaction with'a reagent which containsan epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said latter patent are the following:

om-cn-on-Nn-om OHzCH-CH -NHOH -CHOH The products obtained by the hereindescribed processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture exceptin terms of the process The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial -No. 288,743 and 296,084, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1 The phenol-aldehyde resin is the one that has been It was obtained,

identified previously as Example 2a. from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resinidentified as 2a, preceding, were powdered and mixed with 700 grams of xylene. The mixture was refluxed .until .solution 'was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. .The formaldehyde used was a 37% solution and grams were used which were added in about 3 hours. The mixture was stirred vigorously and kept Within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phaseseparating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of un reacted formaldehyde'noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours Since the resin.

9 'after the refluxing was started. As soon as the odor of formaldehyde'was no longer detectable the phase-separating trap was set so as to eliminate all Water of solution and reaction. After the water was eliminated part of the Note that in Table H following there are a large number of added examples illustrating the same procedure. In each case the initial mixturewas stirred and held at a fairly low temperature (30 to 40 C.) for a period of xylene was removed until the temperature reached about several hours. Then refluxing was employed until the 150 C. The mass was kept at this higher temperature odor of formaldehyde. disappeared. 7 After the odor of for about 3% hours and reaction stoppe Dllflng formaldehyde disappeared the phase-separating trap Was mnefmy adfhtlonal water Whlch fagprobably Water of employed to separate out all the water, both the solureaction which had formed, was elunmated by means of d d Aft H th h d b the trap. The residual xylene was permitted to stay in Ion an con ensa er a water a een the cogeneric mixture. A small amount of the sample Separated enough Xylene was a en 011i 0 have the final was heated on a water bath to remove the excess xylene product reflux for several hours somewhere in the range 311d the retsldual glatelgaii fii is fzl t k 3 of 145 to 150 C., or thereabouts. Usually the mixture e cons1s ency o a s 1c y m or a -ac y resin. e iel'ded a clear' Solution b the 4 me e bu overall'reaction time was a little over 30 hours. In y n fth t th p the Water other instances it has varied from approximately 24 to 36 or a a l f hours. The time can be reduced by cutting the low tem- N a as P p 9 Prevlously thls F' is perature period to about 3 to 6 hours. illustrated by 24 examples in Table II.

TABLE r1. 1

Strength of Rea R 4, Ex Resin Amt, Amine used and amount formalde Solvent used tion tih ri (ii gill No used grs. hydesoln. 811d 8011:. temp, time, tem

and amt. C. hrs.

1b 2a 882 Diethanolamine,210g 377 162 Xylene 7 00 22-2 2 2b.. 5a. 480 Diethanolarnine, 105 g. 37%3181 gin Xylen :450 5.". 21-22 28 102.. 633 do do Xylene.60 20-22 36 145 4b-.-" 2a. 441 D1propanola7nine,133 g y e 0 g 20-23 34 146 5b 5 4 0 d Xylene,450 21-23 24 141 6b 10a 633 do I d Xylene,600g 21-28 24 7b- 2a 882 Ethylethanolarnine,178g 37%,162g y e e,70o 20-26 24 152 8b"-.- 5a.-..- 480 Ethylethanolamine,89 g 37% 81g Y 0 g 24-30 28 151 9b- 10am. 633 do Y o 22-25 27 147 100.--. 13 473 Cycolhexylethanolamine,143g Y e,45o 21-31 31 146 11b 14a 511 do o-..-, 22-23 36 148 120.". 1511.--. 665 do do e ,550g-- 20-24 27 152 130.-.- a 441 ogmoornlocmi '7 NH, 176 g. xy1ene,4oo 21-25 24 HOC2H4 I 140.--- 5a-- 480 c,H5o04H4OOn NH, 176 g. d Xylgn Am g 20-26 26 146 HOCaH;

15b 9a 595 CQH5OCQH4OO2H4 H. 176 g. do x len sso u 21-27 so 147 HOCzHi i 2a.-- 441 00 ,00,H4OC2H4 N, 192 g. ;a0 j. xy1en. 2M2 .1 11002111 5a 480 HOC2H4002H4OC2H4 N, 192 g. do 20-25 28 150 1%.... 1411-.-- 591 HOC2H1OC2H4OCH4 N, 192 g. do xylgne,5()og 21-24 32 149 2211---- 49s HOC H OO2H4OOzH4 .1

N. 1022 35mm, 4m--. 22-25. 32 158 CH:(OC2H1)3 N, 206 g. 3095.100 gr. Xy le ne,500g 21723 36 151 210-..- 2511---- 547 ;GH (OC2 4)z N, 6 e-- do do 25-30 34 14s HOCIHL 441 CHKOCQHO:

.20eg. ..---do. Xylene,400g 22-23 1 146 11001111 64.--. 595 Decylethanolamlne 201g 372 $1 X15119 50o 22-27 24 145' 24b 27a. 391 Deeylethanolamme: 100g g x1ene30o 21-25 26 147;

3 about 15'to 20 pounds.

' 7 product, to wit, 1'1.16jpounds.

' j n I PART 5 v I In preparing oxyalkylated derivatives of products' of the kind which appear as examples in,Part 3, ,I havefound it particularlyadvantageous to -.uselaborato ry equipment which permits continuous:oxypropylation'and oxyethylaition. V v p V with glycide subsequently in the text. The oxyethylat on T step' is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. .What immediately follows refers to oxyethyla- More specific reference will beinade to treatment tion and it is understood that oxypropylation can be handled conveniently in exactly the same manner. The

oxyalkylation of the amine resin condensate is carried. outby procedures which are commonly used for-the oxyalkylation of oxyalkylation susceptible materials. The

. ,factors to be conside'red are discussed in some detail in applications Serial No. 301,304 and: 310,552 and reference is made to those 'applicationsfor a de'scription of .suitable equipment, precautions to be taken and a general discussion of operating technique. 'The following ex- 7 amples are given by way of illustration.

Example 1 V -The oxyalltylation-susceptible..conipound'employed is the one previously'described' and designated as Example 1b. Condensate 1b was in turn obtained from diethanolamine and the resin previously identified'as Example 26;.

' Reference to Table I shows that this particular'resin'is' obtained from parater-tiarybutylphen'ol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in solvent remained the same.

was another 11.16 pounds, all addition of oxide inthesc i various. stages being based on the addition of this.par-.

' ticular amount.

- 12 a fmained the same, to wit, onepound, andthe amounthf The amount of oxide added Thus, at the end of the .oxyethylation step the amount of oxide added wasa total of 22.32

7 pounds and the molal'ratio of ethylene oxide .to resin conr to wit, 2 hours.

oxide added again was 11.16 pounds. There was no 7 7 pounds of solvent (xylenelaloug with one :pound of 1 finely powdered caustic soda as a catalyst; -Adjustme'ntwas made in the autoclave to operate at a temperature of approximately 1251C. to 135 C.,'and at a pressure of The time regulator was set so as to inject'theethylene V oxide in approximately two hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact,"the:oxide was taken up almost immediately; Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at I ,were concerned were the same as in previous examples.

the low pressure, undoubtedly was due ina large measure cerned and also for the purpose o'f making some tests on x various oil field emulsions.

"The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the -data presented in tabular form in subsequentrTables 3 and 4. 7 The size of the autoclave employed was "25 gallons. 'Ininnumerable comparable oxyalkylations I have withdrawn a substantial portion at' the end of each step and continued oxyalkylation on aEpartitl residual sample. n This was not the case in-this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

' This, example simply illustrates the further oxyalkylation of Example 1c, preceding. As previously stated, the

oxyalkylation-susceptible compound to wit, Example 1b; present atthe'beginning of the stage. was obviously the a same as at the end of the prior stage (Example 1c), to "wit, 11.16 pounds; The amount pr oxide'present'in 'the initial step was 11.16 pounds, the amount of catalyst 'redensate was 50.8 to 1. The theoretical molecular weight l was 3348;

The maximum temperature during the operation was C. to C. The maximum pressure was in the range of15 to 20 pounds. The time periodwas one hour;

Example ,The oxyalkylation' proceeded in the same manner There was no? added solvent and noa-dded catalyst. The oxide addednwas scribed in Examples 10 and 20.

11.16 pounds and the total oxide at the end of the oxyethylation step was 33.48 pounds.

oxide to condensatewas 76.2 to 1. Conditions as far as temperature and pressure and time were'concerned were all the same as in Examples 10 and 2;. period was somewhat longer than in previous Examples,

. Example 40 The oxyethylation was continued and the amount of added catalyst and no added solvent. The theoretical molecular Weight at the end of the reaction period was 55 80. The molal ratio of oxide to condensate was 101.6

to 1. Conditions. as far as temperature and pressure The time period was slightly; longer, to wit, 3 /2 hours.

The reaction unquestionably began to slow up somewhat.

Example 5 c The oxyethylation continued with the introduction or another 11.16 pounds of'ethylene oxide. No more solvent was intr'oduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agi t'ation period was 6696, and the molal'ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. pressure remained the same as in the previous example.

Example 60 The same procedure'was followed as in the previous examples except that an added pound of powdered caustic soda wasintroduced to speedup the reaction. The amount of oxide added was another 11.16 pounds,

bringing the total oxide introduced. to 66.96 pounds. The

temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2 /2 hours.

' Example 7 c The same procedure was *followed as in the previous six examples without the addition of more caustic or more solvent. 7 end of the period was 78.12 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8928 The time required for the oxyethylation was a bit longer than in the previous stop, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solventand no added catalyst. The total amount of oxide added at the 'end of this step was 89.28 pounds; The theoretical molecular weight was 10,044. The metal ratio of oxide' to resin condensate was 203.2 toone. Conditions as 'far'as temperature and pressure were concerned were the same as ethylation was 4 hours.

in the previous examples and the time required for oxy The .molal ration of The time Operating temperature and The total amount of oxide introduced at the The same procedure as described in' theprevio'us examples are employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a l-gallon autoclave and then transferred to a ZS-gallon autoclave. This is immaterial but happened to be a matter of convenience only. 'The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds through 40c were obtained by the use of ethylene oxide, whereas 41c through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as

happens to be the case in Examples 10 through 40c, theamount of oxide present in the oxyalkylation derivatives is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caus: tic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period. I

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 1c, 20, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes .place.

Referring to Table IV, Examples 41c through 800 are the counterparts of Examples 1c through 400, except that the oxide employed is propylene oxide inside of ethylene 14 oxide. Therefore, as explained previously, four'oolurrms are blank, to wit, columns 4, 8, 11 and 15.

Reference .is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d.- They are derived, in turn, from compounds in the 0 series, for example, 350, 39c, 53c and 62c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 35c and 39c, involve the use of ethylene oxide first, andpropylene oxide afterward. Inversely, those compounds obtained from 53c and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 35c, 39c, 53c, and 620 were duplicated and the oxyalkylati'on stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32:1, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 350, consisted of the reaction product involving 11.16 pounds of the resin condensate, 16.74 pounds of ethylene oxide, 1.0 pound of soda, and 7.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16a, and oxypropylation for 17d through 32d.

It Will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtainwhat may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, of any other variant.

Needless to say, one could start with ethylene oxide andthen use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless ydroalinity' gen radical the presence jectionable or else add a is comparatively small and it need not be re- Generally sp eaking, the amount of alkaline catalyst The preferred procedure isto' ignore there is no 1 justification for the cost of bleacbing th'e product present 7 moved.- Since the products per se are alkaline due to a the presence of a'basic nitrogen; atom, therembval of the alkaline catalyst is somewhat more difiicult than ordinarily is the case for the reason that if one'addsh chloric acid, for example, to neutralize'the alk 10 one may partially neutralize the ,basic nitro also. of the-alkali unless 7 it is ob stoichiometric amount of concentratedhydrochloric acid equalto the caustic soda presentf TABLE III Products can be pre-7 7 -15 I 7 7 tially'and the resins themselves maybe yellow, 7 7 amber; or even dark amber. Condensation'of a nitrodarker colored aromatic petroleum V Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the resins ini genous product invariably yieldsa darker product than the original resin andlusually has a reddish color. The solvent employed, if xylene, 'adds nothing to the color 5 but one may use "a 7 solvent;

1i hter the'color of the product. pared in whi h the final color is a 1i hter amber Wish a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, orsome other industrial uses,

1 v 7 7 5. 7 v 7 7 7 7 7 t 7 7 7 7 1 84 628400000000 82604826 284O628442086 WHO 7 1 284024620000000 a 346 9124050565 565 2 751628394073940 20c a M MWMMM 23456790570257M212$4Wmm675702570362739405 M MMWM %MN%MMWMMW 7 W%W %U OWM fiM 2&4 5 & 6 &02 3 5 hw7 & 0'LOM &4 5 Q- &Q 2 QW:WQZ&QLLazomdml xwfifi owfi mfl 2 3w4'5 6 2 2 3 5 6 S 1 3 H 1 7 7 11 11 n 11 l M 7 oo 7 7 7 M om 7 1 W 7 .7 t 3 680 5 7 50762 7 2 7 le L eyL 7 8 8/0 4. 0 Ddxy 0 dx 7 v um m n0&mm fi mflommm NMMW%MQ QMHM M 7 1 r P m wc m P m we l 1 a a N a wwmd m wnma u n n u 061727 864 0 6 49 89082687542198 580 no 1 e M mho mm 570257m253m4m9 24%9247925814793H235$7W0 M mflo c u n n 11112 11112 1111 11112 1 E t no 7 7 7 7 E au 7. M S 7 7 M S e 00000000555555 05000000005555555566000000 e 0OOOO0O05555555 M am M 71777111444444Arm- 777IFLTZA A-4 4A 7A 4L- 77L TZTZ M n M 7 7 7 7 7 7 7 7 44-4M74 A74 4- 7 S 1 ,7 7 7 7 8 7 7 H V .l. 7 o w v M 7 H 7 7 m .w y 0 000333300003333000033330000333300003333 m 1 111114441111155 1L LLL1LLLLLLLL1LLLLLLLLLLLLLLLLLLLLLLLLL W LLLLLLLLLLLLLLL. m C1 7 m l 7 0 0 O O O 7 M I 4 4 V 6) Wd n n n n n u n u n n n u n n H n D s 7 mi 2 PM u h u n PM 1 a 7 7- 17 623406 8 O0 0 48260482628 0628 642086 7 l ti 23456 9257 257 12 45562570257 51627 94 t1 EM 234 56ml 8123m 78mm23P 56- 81235678m 11.22%34 m w .7 7 n 66666 600 O O 444 6666666666 66 1 n 7 Wd 11111MMI55M5W5MMM888$MM$5555 llllmmll E Sds mwwmmwmmmwmwwmw 7 b LLLLLILLZlZZZlnA QQQQQQQQZZZZoLlZZ LLLLLLLL L b LLLLLLLLZZZZZZZ Om 111111111111111 11111111111111111111111 B 0m] 111111111111111 C 7 7 A 7 7 7 000000005555555500000000555555.5500000000 T 1 000000005555555 7 ,7 mm 7 7 17711744 24 4114111711114444444411711111 mms 7 111111144 44444 7 V 7 7 c 7 W 7 7 w y 00003333000033 33000033330000333300603333 1 1111144411 115. 0 7 W ILLLLLLLLLLLLLLLL LLLLLLLLLLLLLLLLLLLLLLL mfi w TTLLLLLLLLLLLLLI 7 7 7 CW... :A 7 L I I 8 8 I 1 7b mum m wm n Xl n X 0 P0 7 0 P0 m 7 a S i .6234 62 .1 .7 r O mm 516.2%39 m m am n p h 7 7 E w m 0 C m C 7 t e 1 awn m 7 6 m 7 Om so m] n c u O 1 .1 1 0 d t d wm wPN O L Z n w w 0 X 0 N 0 N 7 1 x 7 v E 7 E TABLE VI (continued) Max. Max. Solubility Ex. temp, pres, Time, No. F C. p. s. 1. hrs.

Water Xylene Kerosene 15-20 6 I '15-20 1% Ibsoluble.

15-20 1% .d Dispersible. 15-20 2 Soluble. 15-20 3* D0. 15-20 4 Dof 15-20 3 D0. 15-20 1 Do. 15-20' 5 D0. -35 Insoluble. 25-35 1% Dispe'rsiblel 25-35 2" D0. 25-35 3 Soluble. 25-35 4 Do. 25-35 3% Do. 25-35 4- Do; 25-35 5 1 D0.

5-10 2 Insolublev 5-10 2% Dispersible.

5-10 3 Soluble.

5-10 5 I Do. 15-20 Insoluble 15-20 D0. 15-20 1 Dispersible 15-20 2 Soluble. 15-20 3- Do. 15-2o 2%: Do. 15-20 3= Do. 15-20 4 Do; 15-20 2 Y Insoluble; 15-20 D0. 15-20 1 Do. 15-20 2 Dispersible. 15-20 3 1 soluble'. 15-20 3 Do.; 15-20 3% Do. 15-20 4: Do. 15-20 Insoluble 15-20 Do. 15-20 1 D0. 15-20 2 D0. 15-20 3 Do'. 15-20 3 I Do. I 15-20 3 Dispersible I 15-20 oluble.

15-20 A Insoluble. 15-20 Do; .15-20 1 Do. v15-20 2 D0. 15-20 I Do. ,15-20 Do.

15-20 Dispersible. 15-20' Soluble.- 25-30 Do. 25-30 Do. 25-30 Do. 25-30 Dispersible'. 25-30 Insoluble; 25-30 I Do. 25-30 Do;

25-30 M .'....(10 IDo,

5-10 Insoluble Soluble.

5-10 Djspersible.

5-10 Insoluble.

5-10 I Do.

21 PART 6 The conversion of the oxyalkylated basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, if required, is ignored in subsequent Table No. VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts or, at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuation-in-part of certain co-pending applications and reference is made to aforementioned copending aplication, Serial No. 329,483, filed January 2, 1953. The co-pending application, Serial No. 329,483, filed January 2, 1953, describes the neutralization of the nonoxyalkylated condensate. Reference now is made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the amount of gluconic acid (50%) required to neutralize a certain amount of condensate, for instance, compare Example la in Table VII with Example 1b in Table II. In any event since there were available various oxyalkylated derivatives of condensates lb, 517, and 7b, these particular oxyalkylated derivatives were used for the purpose of illustrating a salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example If in Table VIII it is to be noted that 1116 grams of the nonoxyalkylated condensate required 756 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1116 grams of the condensate 11 when converted into the oxyalkylated derivative as obtained from So were equivalent to 5150 grams. Therefore, 5150 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate generally is a liquid and, as a rule, contains a comparatively small amount of solvent. Note the examples in Table VIII. ,The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Needless to say, the solvent could have been removed from the oxyalkylated derivative by use of vacuum distillation and this is particularly true if benzene happened to be the solvent. The product obtained from oxyalkylation is invariably lighter than the initial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color or an amber shade with a reddish tint.

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol,

to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mix-' ture to reflux action under a condensate or a phaseseparating trap. If there happened to be any tendency for the product to separate then the solvents having hydrotropic properties, such as the diethylether of ethyleneglycol, or the like as used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the proauctrs diluted to approximately 50%, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxalkylated derivative. the product is used there is no justification for the added cost of decolorization. The salt form can be dehydrated I or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phase-separating trap.

The product as prepared, without attempting to de-- colorize, eliminate any residual catalyst in the form of a salt, and without any particular etfort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demulsifier for petroleum emulsions of the water-in-oil type, or oil-in-water type; or in the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalkylation may be solids but are generally viscous liquids or liquids which are almost solid or tacky. Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to polyglycols, of course depending primarily on the amount of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in the majority of cases are liquids. Needless to say, if a solvent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and the simplicity of salt formation it does not appear that any illustration is required. However, previous reference has been made to Table VIII. The first example in Table VIII is Example If. The following is more specific data in regard to Example If.

Example If The salt was made from oxyalkylated derivative Example 3c. Oxyalkylated derivative 30, in turn, was made from condensate Example 1b. Condensate Example 1b,

in turn, was made from resin Example 2a and diethanol- For various commercial purposes in which with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that Conventional demulsifying agents may be used in awater-soluble form, or in an oilsoluble form, or in a form exhibiting both 'oiland watersolubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However,.since such reagents are frequently used in a ratio of '1 to 10,000 or 1 to 20,000, or 1 to 30,000,0r. even 1 to 40,000, or 1' to 50,000 as in desalt'ing practice, such an apparent insolubility in oil and water is not significant because 7 diluted to approximately 50% with xylene and employed 'intheform of a 50% solution. 7

A number of other examples are included in Table 10 VIII. 7 V i For convenience, Table VII is. included at this point just preceding Table VIII.

TABLE v11 7 Salt formation calculated on Condensate in turn derived from basis of non-oxyalkylated Salt condensate from Salt, con- Ex, den- 37% Wt. of No. sate Amt. Amt. Amine formconden- Theo 50% glu- No. Resin resin, Solvent sol- Amine used used, aldesate on basic conic N o. gms. vent, gms. hyde, solventnitrogen, acid,

gms. gms. free basis, gms. gins.

e .gms.

882 Xylene.. 882 210 162 1, 116 27. 756 480 do. 480 0 105 81 597 13.5 378 633 -do 633 6.56.; 105 81 750 13.5 378 441 do. 441' Dipropanolamme. 133 100 586 13.6 380 480 do 480 .do 133 100 625 13.6 380 633 '.do 633 '.do 133 100 778 13. 6 380 882 .do 882 Ethyl-ethanolamine 178 162 e 1, 084 28.0 784 480 ..do 480 do 89 81 581 14.0 392 633 do. 633 --do' 89 81 734 14.0 392 473 do 473 Cyclohexyl-ethanolamine 143 1 100 671 14.0 392 511 do 511 do 143 81 728 14.0 392 665 do 665 do 143 81 882 14.0 392 882 do. 882 Diethanolamlne 210 162 1, 116 27. 0 378 y 441 do 441 Dipropanolamine- 1 100 586 13. 189 152---, 7b 882 .do ,882 Ethylethauolamine- 178 162 1, 084 28.0 392 1 formaldehyde. 7 g

' TABLE VIII Grams of oxyalkyle ated compound 7 Obtainedin turn from Percent which is equiv. percent Oxyalkyl- 7 condent0 grams of congluconic Ex. No. ated desate in densate acid to rivative, oxyalkylneutral- .ex. N o. ated de- 7 ize, grams Oonden- Amt. con- EtO PrO Solvent rivative Oxyalkyl- Condensate, densate, amt., amt, amt eted comsate ex. N0. lbs. lbs. lbs. lbs. pound said reagents undoubtedly have solubility within such' concentrations. This same fact is true in regard to the material or materials employed as the demuls'ifying agent 7 of my process,

In practicing the present process the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying including batch, continuous, and down-the hole demulsification, the process essentially involving introducing a small amount of demul'sifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the'mixture to stratify.

PART 7 Conventional demul'sifying agents employed in the treatment of oil field emulsions are used as-sucb, or after a dilution with any, suitable solvent, such as water, petroleum' hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, .particw 'larly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol,'etc., may be employed .as diluents. Miscellaneous solvents .such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refiningfof petroleum, etc., maybe employed as diluents. Similarly, the material or materials employed as the de-. mulsif'ying agent of my process may be admixed withone r ornrore'of the solvents customarily used in connection As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following: Oxyalkylated derivative, for example, the product of Example 30, 20%; t

Acyclohexylarnine salt of a polypropylated naptha' lene monosulfonic acid, 24%;

An ammonium salt of a polypropylated monosulfonic acid, 24%; l

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, E

The above proportions are all weight percents.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic o-xyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula V napthalene in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which. R is any aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic 'hydroxylated secondary rncnoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactantshave contributed part of the ultimate t molecule; and with the further proviso that the resinous condensation product resulting from the process be heat- I stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene'oxide having not more than 4 carbonatoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylg lycide.

i 3 A process for breaking petroleum emulsions of the water-in oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over-8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence 'of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom,

and (c) formaldehyde; said'condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide,

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting "the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkyl-ationsusceptible, fusible, non-oxygenated organic solvent.- soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nucleiper resin molecule; said resinbeing difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenoland an aldehyde having not over 8 carbon atoms and reactive toinwhich R is an aliphaticchydrocarbon radical having at least 4 and not more than 24 carbon atoms and substitutedlinthe 2,4,6 position; (b) a basic hydroxylated'secondary monoa'mine having not" more than 32 carbon atoms in any group'attached to'the amino nitrogen atom,

ans-(a fornraldehydmsaid condensation reaction being conducted atatemperature suflicientlyhigh to eliminate water and below tthe pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of 'the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the molar'ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous'condensation product resulting 'from the process-be heat-stable and oxyalkylation-suscep-tible; followed by an oxyalkylation step by means of an alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

5. A process for breaking petroleum emulsions of the ,w'ater-in-oiltype characterized 'by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the processof condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

' water-insoluble, low-stage-phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a di', functional monohydric phenol and an aldehyde having not over 8 carbon atoms vand reactive'toward said phenol; saidresin being formed in' the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated c secondary monoamine having not more than 32 carbon atomsin any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature 'Sufiiciently high to'eliminate product resulting from; theprocess be heat-stable and oxyalkylations'usceptible; followed by an oxyalkylation step by means of an a'lpha beta alkylene oxide having not consisting of ethylene oxide; propylene oxide, butylene oxide, glycide and methyl-glycide.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a dernulsifier including the gluconic acid" salts of the basic oxyalkylated products obtained in turn in the process of condensing (a), an oxyethylation-sus ceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenol formaldehyde resin having an average molecular weight corresponding toat least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said .phenol being of the,

formula V t OH in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted ata temperature sufficiently high toeliminatewater and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensa tion reaction be conducted so as to produce a significant portion of the resultant in which each of the-three re actants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge conmeeting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1,2 and 2 respectively; with the further provisothat said procedure involve the use of a solvent; and with the final provisothat' the'resinous condense tion product resulting from the process be heat-stable 'and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

7. 'A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin'molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunc-tional phenols; said phenol being of the formula stituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having notmore than 32 carbon atoms in any group attached to the amino nitrogen atom,

and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate V waterand below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the more than4 carbonatoms and selected from the class '75 condensation reaction be conducted so as to produce a ysignificantportion of the. resultant imwhich each ofvthe three reactants have contributed part .of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by 1 an oxyalkylation step by means of analpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and-methylglycide.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion ;to the action of a demulsifier including the gluconic acid :salts of the basic oxyalkylated products obtained inturn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over phenolic nuclei per resin molecule; :said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional mcnohydric phenol and formalsdehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the'formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived .methyl- .ene bridge connecting the aminonitrogen atom with a resin molecule; with the added proviso that the'molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic. hydrocarbon radical having. at-least4 and not more than 14 carbon atoms; (b) a basic hydroxylated secondary monoamine having not more than32 carbonatoms in any groupattached to the amino nitrogen atom, and. (c) formaldehyde; said condensation reaction being conducted=ata temperature above the boiling point of water and below C., withthe proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each ofthe three reactants havecontributed part of the ultimate molecule by virtue ofta formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; withthe added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with thefurther proviso that said procedure involve the use of a solvent; and with the final proviso thatthe resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxidehaving not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

10. The process of breaking petroleum emulsions as defined in claim 1 wherein the oxyalkylation step of vthe manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The process of breaking petroleum emulsions as defined in claim 2 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

12. The process of breaking petroleum emulsions as defined-in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both-ethylene oxide and propylene oxide in combination.

14. The process of breaking petroleum emulsions as defined in claim 5 wherein the oxyalkylation step of the manufacturing process is limited to the use'of both ethylene oxide and propylene oxide in combination.

15. The process of breaking petroleum emulsions as defined in claim 6 wherein the oxyalkylation step of. the

manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

16. The process of breaking petroleum emulsionsnas defined in claim 7 wherein the oxyalkylation step of'the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

17. The process of breaking petroleum emulsions as defined in claim 8 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

18. The process of breaking petroleum emulsions as defined in claim 9 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

19. The process of claim 1 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

20. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of Xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

21. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the' oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said volumes of water.

xylene solution isshaken vigorously with qnehto three -volumes'ofwater. r

22.; The process'of claim 4'with the proviso that the. *hydrophile properties of the gluconic acid saltdfthe "oxyalkylated condensation product in an equal weight of xylene are suificient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

23. The process of claim 5 with the proviso that the hydrophile properties of the gluconic acid salt of the 'oxyalkylated condensation product; in an equal weight of xylene are s uificient to producegan emulsion when said xylene solution is shaken vigorously with one to three volumes of water. V

24. The process of claim 6' with the proviso thatthe hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three =volumes of water. 1 g f 25. The process of claim 7 with theproviso that the 'hydrophileproperties of the gluconic, acid salt of'the I "oxyalkylated condensation product in an equal weight of xylene are suflicient to produce'an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

26. The process of claim 8 with the proviso that the hydrophile properties of the gluconic' acid salt of'the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. e

27. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three 28. The process of claim 10 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said 2,031,557 Bruson Feb. 18, 1936 2,449,365 De Groote et al Mar. 7, 1950 2,535,380 Adams et al. Dec. 26, 1950 2,542,001 De Groote et a1. Feb. 20, 1951 2,545,692 Gleim Mar. 20, 1951 2,568,739 Kirkpatrick et al. Sept. 25, 1951 2,679,485 De Groote May 25, 1954 2,695,888 De Groote Nov. 30, 1954 oxyalkylated condensation productin an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one tothree volumes of water.

I 31. The process of claim 13 with the proviso thatthe hydrophileiproperties' of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. a a V V V 32. The process of claim 14 with the proviso thatthe hydrophile properties of the gluconic acid salt of-the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. I

33. The process of claim 15 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

34. The process of claim 16 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sulficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. g

35. The process ,of'claim 17 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

36. The'pro'cess of claim 18 with the proviso that the 'hydrophile properties of the gluconic acid salt of the oxyalkylatedcondensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

7 References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC OXYALKYLATED PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE: SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 